Acridone dianthrimide vat dyestuffs and their production



Patented May 14, 1935 Ivan Gubelmann and Robert J. Goodrich, South Milwaukee, and Wis, assignors,

William, Dettwyler, Milwaukee, w by'mesne assignments, to E. I.

du Pont de N emours 85 Company, a corporation of Delaware No Drawing. Application April 30,1931,

Serial No. 534,134.

17 Claims. rm-.37)

i ,This invention relates to a process of condensing ;a halogen anthraquinone acridone containing halogen in the B2. nucleus of the acridone group as well as in ,an alpha positionv of the anthraquinone nucleus, with ,an' alpha amino anthraquinone. 1 q

This invention also relates .to the products produced by the process and includes their substitution products and derivatives. 7

It is an object of ,this invention to provide a method of preparing anthraquinone derivatives which maybe regardedas alpha, alphaf-dianthrimides and in. which one anthraquinone residu'e forms part ofan anthraquinone-acridone l5 residue of the following structure (halogen)= II i 2 (x= 1 or more) Clz 45 l H1 H i 50f Ann-aw V i 1 1 01 0 NH-R(a) wherein It stands for a1 1, anthraquinone residue, subs t t d n More specifically,

readily react with The products of our invention are/in themselves dyestufis but-can also be used as intermediates ior the preparation of other vat dyestuffs. The .Bz-halogen "acridonyl alpha-a1pha-dianthrimides of 'our invention are distinguishable,

from and superior to the similar acridonyl alphaalpha-dianthrimides not containing halogen in the 32 ring because of their commercially valuable shades and their good fastness properties. One of their most important qualities is'that they 'are capable of being converted into other very valuable dyestuffs. v

' It is known in the literature that polyhalogen anthraquinone-acridones containing three or more halogens in the molecule are converted into or inorganic bases or salts of Weak acids in the presence of a copper salt. For example, a trichlor-anthraquinone-acridone heated in nitro QFFICE products containingv lesser amounts of halogen upon heating to high temperatures with organic benzene in the presence of sodium acetate and copper oxide is convertedinto'a mixture of mono and dichloro-anthraquinone-acridones. We have now found that this reaction can be made to proceed'in another direction where the'baseemployed is an amine such quinone, its derivatives or substitution products. when the starting materials employed are v halogenated 1,2 -anthraquinoneacridones, which in addition to gen in the 32 ring of the acridone group also contain halogen in an alpha position of the-anthraquinone residue, the final product is a 1,2-acridonyl-alpha, alpha-dianthramide. This reaction was not to be foreseen since it is known in the as alpha amino anthracontaining halos art that Bz-halogen anthraquinone-acridones amino-an'thraquinones exchanging one of the Bz-halogens for the aminoanthraquinone residue. It was therefore to be expected that in the case of halogen-anthraquinone-acridone bodies containing halogen in the anthraquinone residue as well as in the Bz nucleus, Bz-substitution would takeplace at least to some extent, if not exclusively.

As a result of this preferential reaction of the alpha amino anthraquinones with the halogen in the alpha position of an anthraquinone residue containing an acridone ring there is opened up a field or" entirely new dyestuffs possessing outstanding properties such as new shades possessing excellent fastness qualities.

The following examples are illustrations of the manner of effecting theabove reaction. These examples are merely representative of the general process of our invention, and We do not propose shades.

cottonfrom a bluish The product obtained has most probably the folto limit ourselves to the specific details or starting materials disclosed. The parts given are parts by weight.

. Example 1 20 parts of tri-chloro-anthraquinone-acridone prepared by passing chlorine into 1(N) ,2-anthraquinone-acridone suspended in nitrobenzene in the presence of a small amount of iodine at.

100 C. until evolution of HCl'ceased (chlorine content 23-24%) are added to 200 parts of nitrobenzene. There are next. added 12 parts of alpha-amino-anthraquinone, 20 parts of sodium carbonate, and 6 parts of verdigris. Thas mass is heated to the reflux temperature with stirring for about 5 hours. It is then cooled to room temperature, filtered, and the filter cake washed with a small amount of nitrobenzene, and finally with alcohol. It is then dried. The darkpowder obtained is soluble in concentrated sulphuric acidwith a reddish brown color andto the best ofhour understanding correspondsto the following formula: i I

It dyes cotton from' a. bluish violet vat in gray p Example-2 Y To; 200 parts of nitrobenzeneiare added 20 parts .of;.the halogenated anthraquinone acridone Example 1); 13 parts of l-amino- 2.-.methy1-anthraquinone, 20 parts of soda ash, andr6- parts of verdigris. The mass is refluxed for. hours underagitation. It is then cooled to room; temperature, filtered; and the filter cake washed-with a small amount of nitro-benzene and finally with a little alcohol, and then dried. The product obtained is soluble in concentrated a red brown color and dyes violet vat in gray shades.

sulphuric acid with lowing formula:

We are aware that the conditions effecting the anthrimide condensation may be altered considerably to produce similar results and we do not propose to limit our invention to the specific methods setforthzin the examplesi For example, other high boiling diluents' than nitro-benzene may be used as well as other temperatures of reaction and other copper salts than verdigris. Similarly, instead: of: the particular amino-anthraquinone bodies disclosed, other alphaamino-anthraquinone bodies may be used, provided' of course they contain no substituents which are more reactive toward halogen than the amino groupg-as. will be obvious to anyone skilled in the art. Moreover, in view of our discovery I that the reaction is one of anthrimide formation, in other words, in view of the fact that halogen in the alpha position of the anthraquinone nucleus is replaced by an anthraquinonyl amine residue in preference to the halogen in the Bz nucleus of the acridonering; any-method suitable for making anthrimides may"be-used 'without departing from thescop= of the invention:

We claim as'our invention? 1. The process alpha-alpha dianthrimide containing .halogenain the B2 nucleus which comprises-iheating; anialpha amino anthra quinone with a. poly-'halogenzianthraquinonelzeacridone-. having halogen; in? the B2 nucleus and in: an thraquinone nucleus; r A

2. The process of claim 1", in wliichlthevreaction is carried outin the: presence ofiaehi'gh boiling inert solvent, a copper catalyst andi an acid binding agen I 3. The process of preparing a ing the following formula:

compound hav- -(halogen)a Nix-Rab 1 in which R represents ananthraquinone nucleus, which comprises heating an-alpha amino anthraquinone in a high boiling inert solvent with a compound having the following formulas- H easiest.

halogen I 4. The process of claim 3, in which the: high boiling: solvent is nitrobenzene and in which the 1,2-acridonyl-4-alpha' -dianthrimide", wmurcom- W prises heating an alpha amino anthraquinone with a tri-halogen anthraquinone acridone having the following. formula:

Y in thepresence of a a o n I I high boiling inert solvent, a coppercatalyst and an acid binding agent.

G'S -Th'e' process of ing the following formula:

preparing a compound havwhich comprises heating alpha amino anthraquinone with a tri-chloro anthraquinone acridone having the following formula:

in the presence of a high boiling inert solvent, a copper catalyst and an acid binding agent.

'7. The process according to claim 6, in which the reaction is .carried out in the presence of nitrQp-benzene, 'verdigri's and sodium carbonate.

dianthrimides.

9. Bz-halogenated 1,2-acridonyl 4-alpha-dianthrimides having the following general formula:

o NH-R(a) in which R is an anthraquinone nucleus.

anthrimides having the general formulaf (chlorine)n 'in which R is an anthraquinone nucleus? 11.-A- Bz-chlorinated lQZ-acridonyl ll-alpha!- dianthrimide having the following generalfor-' O mula:-

the following formula 4 wherein Y stands for hydrogen or a methyl group rillwhich comprises heating an amino-anthraquinone having the following formula:

NH: O

v v 1'40 V 12.1mm p o e sp ep r qq nq ifi witma: tri olfloroaanthraqulnone ormone of the followingiormulm x V I v 1 in the presence of an ine'i't high boiling solvent, a copper catalyst an'd'an acid binding agent. 1.5; The, proeesssa-coordlng to claim IQYiH WhlC-h a v -t,h inert high:hoillng:solvent-1is.;.ni1;1;0b y1 -a phaf-di- IBLThe cOmpQundsf: the iollowingi anthvimidesvhaving' the following, general for- ,formula mulaw: a

in which A is an alpha anthraquinone radical and X is halogen.

17. The compound; of the'nfollowing general 35 formula wherein Y stands for hydrogen or a methyl :5

4 l fihr .7 a l .0 MZTheprocessofprepai ing a compounw having the following general formula Y P4 65 I which comprisesiheating toboiling with an alpha 1 WAN amino anthraquinone a trichloro anthraquinone 3 ROBERT L .,GQQ1JRICH; acridone having the following formula 7 WILLIAM Certificate of Correction Patent No. 2,001,418. Ma 14, 1935.

" IVAN GUBELMANN ET AL.

It is hereby certified that error appears in the printed specification of the above nurnbered patent requiring correction as follows: Page 3, second column, lme 46, claim 12, at the extreme upper right corner of the formula, for C1 read Oh; and

that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 18th day of June, A. D. 1935.

[SEAL] LESLIE FRAZER, Acting Commissioner of Patents. 

